ConspectusOwing to climate change and over-reliance on fossil fuels, the study and development of sustainable energy is of essential importance in the next few decades. In recent years, rapid advances have been witnessed in various power to gas electrocatalysis technologies including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) for realizing the target of blue planet with carbon neutrality. Nevertheless, practical applications with superior performance and affordable cost are largely limited by the electrode materials because the reactions are regularly driven by precious metals such as platinum (Pt) or iridium (Ir) based catalysts. Therefore, it is of significance to develop novel electrocatalysts with high electroactivity and limited cost for boosting the commercialization of green hydrogen technology.Since nitrogen-doped carbon nanotubes were first reported for enhanced ORR performance in 2009, the exploitation of carbon-based metal-free catalysts (CMFCs) as potential replacements for the precious metal electrocatalysts has become an attractive research field. To date, great progress has been made in developing new dopant strategies for CMFCs; however, the details of the catalytic mechanism and identification of active sites remain unclear, owing to the complexity in controlling the dopants and their homogeneity in carbon-based materials. To tackle this issue, our group has presented a series of works on defects catalyzing electrochemical reactions and proposed a defect catalysis mechanism since 2015. This theory is now widely accepted by the research community and has become a very important area in electrocatalysis worldwide.In this Account, we first present the defect theory for the reasonable design of defective carbon-based materials (DCMs) and subsequently summarize our previous works on the state-of-the-art defect engineering strategies to design DCMs possessing high activity, with the particular emphasis on the conjunction between defect structures and electrochemical performances. We also categorize recent defect modulation approaches on active sites in DCMs as well as showcase the advanced characterization techniques to confirm the types and densities of defects in DCMs. Finally, several perspectives on the challenges and future research opportunities of this exciting field are proposed. Remarkably, rapid advances of DCMs possessing both high electrochemical activities and low cost as a new generation of electrode materials may greatly facilitate the deployment of sustainable energy infrastructures.